EP0429830B1 - Method of tanning hides and retanning chrome-tanned leather - Google Patents

Method of tanning hides and retanning chrome-tanned leather Download PDF

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Publication number
EP0429830B1
EP0429830B1 EP90119881A EP90119881A EP0429830B1 EP 0429830 B1 EP0429830 B1 EP 0429830B1 EP 90119881 A EP90119881 A EP 90119881A EP 90119881 A EP90119881 A EP 90119881A EP 0429830 B1 EP0429830 B1 EP 0429830B1
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EP
European Patent Office
Prior art keywords
mol
glyoxal
glyoxylic acid
mixture
water
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EP90119881A
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German (de)
French (fr)
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EP0429830A3 (en
EP0429830A2 (en
Inventor
Ortwin Dr. Schaffer
Karl Dr. Stork
Wolfgang Dr. Reuther
Jürgen Dr. Weiser
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
    • C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/28—Multi-step processes

Definitions

  • the present invention relates to an improved process for the sole tanning of pelts and for retanning chrome leather as well as new water-soluble condensation products and a process for their production.
  • Chrome tanning still plays a dominant role in the tanning process. But tanning agents containing chrome alone cannot make leather for all purposes. For this reason, combination tanning is usually carried out, the main tanning being carried out first with chrome tanning agents such as chromium (III) salts and then retanning with, for example, vegetable or synthetic tanning agents. Vegetable and synthetic tanning agents are also used for single tanning without chrome-containing tanning agents.
  • chrome tanning agents such as chromium (III) salts
  • Vegetable and synthetic tanning agents are also used for single tanning without chrome-containing tanning agents.
  • the object of the present invention was therefore to provide tanning agents with an improved single-tanning effect, so that the use of tanning agents containing chromium can be dispensed with, or at least to use these agents to bring about the fact that, in combination with chrome tanning agents, the above-described deficiencies in the prior art are eliminated becomes.
  • condensation products of melamine with glyoxal and / or glyoxylic acid are known, which may contain compounds with a phenolic hydroxyl group or nitrogen compounds. These condensation products are recommended as tanning aids for a chrome-free tanning process, but always in conjunction with tannins containing aluminum, titanium or zircon.
  • FR-A 2 262 056 discloses condensation products made from 0.25 to 0.9 mol of urea and 1 mol of glyoxal. They are recommended as tools for coating paper.
  • Component A is preferably melamine, dicyandiamide, urea or thiourea alone or a mixture of 50 to 95 mol% melamine and 5 to 50 mol% dicyandiamide.
  • Component A is preferably melamine, dicyandiamide, urea or thiourea alone or a mixture of 50 to 95 mol% melamine and 5 to 50 mol% dicyandiamide.
  • mixtures of melamine and urea, melamine and thiourea, dicyandiamide and urea, dicyandiamide and thiourea and urea and thiourea and a mixture of three or four of the compounds mentioned can also be used.
  • Glyoxalic acid or an aliphatic dialdehyde with up to 6 carbon atoms such as, for example, glyoxal, malondialdehyde, succindialdehyde, glutardialdehyde or adipindialdehyde, are used as component B.
  • Glyoxylic acid, glyoxal and glutardialdehyde alone and mixtures of glyoxylic acid and glyoxal and of glyoxylic acid and glutardialdehyde are particularly preferred, the two constituents being present in each of these mixtures in a proportion of 1 to 99 mol%, preferably 20 to 80 mol% .
  • the sum of all components B is between 0.5 and 12 mol, preferably 2 and 7 mol, per mol of A.
  • the glyoxylic acid can be used as the free acid or in the form of its alkali metal salts or its ammonium salt.
  • phenols such as phenolsulfonic acids, sulfosalicylic acids, salicylic acid, resorcinol, pyrocatechol, hydroquinone, hydroxyquinolines or bis (hydroxyphenyl) sulfones and alcohols, in particular carbohydrates such as glucose or starch, are suitable.
  • Acidic compounds can be condensed in the form of their alkali metal salts.
  • Carboxylic acid amides, sulfonic acid amides, carboximides, substituted ureas, amino acids, imino acids and dialkylamines and dialkanolamines can be used as the condensable compound D.
  • Examples include acetamide, formamide, benzoic acid amide, sulfamic acid, Succinimide, phenylurea, glycine, alanine, phenylglycine, iminodiacetic acid, diethylamine, dipropylamine, dibutylamine, diethanolamine or diisopropanolamine.
  • Acidic compounds can be condensed in the form of their alkali metal salts.
  • the compounds C and D are condensed in an amount of 0 to 3 mol, preferably 0 to 0.5 mol, per mol of A.
  • the condensation takes place in aqueous solution at temperatures of 20 to 100 ° C, preferably 30 to 90 ° C, and usually at a pH of 1 to 8.
  • the condensation reaction is in the temperature range indicated usually finished within 10 to 240 minutes. This generally gives clear aqueous resin solutions which can be diluted with water.
  • the solutions obtained are expediently adjusted to a solids content of 10 to 80% by weight, in particular 20 to 60% by weight, and can be used directly for tanning the leather or pelts.
  • the condensation products can also be obtained in powder form by customary processes, such as distilling off the water or by spray drying. If they carry acidic groups, the condensation products can be converted into their alkali metal or ammonium salts.
  • the new water-soluble condensation products mentioned are prepared as described above by condensation in aqueous solution at 20 to 100 ° C.
  • the tanning process according to the invention is outstandingly suitable for tanning pelts alone in an aqueous liquor.
  • the procedure is such that the pickled pelts, for example beef pelts with a gap thickness of 1.5 to 4 mm, at a pH of 2 to 5, in particular 2.5 to 4, and at a temperature of 15 to 50 ° C, in particular 20 to 30 ° C, are treated with an aqueous solution of the condensation products for a period of 5 to 30 hours.
  • the treatment takes place, for example, by drumming in a barrel.
  • the required amount of condensation product is normally 5 to 50% by weight, in particular 10 to 30% by weight, based on the pelt weight.
  • the liquor length, ie the percentage weight ratio of the treatment liquor to the goods is usually 30 to 200%, based on the weight of the naked body.
  • the leather After the treatment has taken place, the leather is usually adjusted to a pH of 4 to 8, for which purpose sodium bicarbonate is used, for example, and, if desired, colored and greased.
  • the tanning process according to the invention is also outstandingly suitable for retanning chrome leather in an aqueous liquor. It is usually carried out in such a way that the pickled pelts, for example beef pelts with a gap thickness of 1.5 to 4 mm, with a conventional chromium-containing tannin, for example chromium (III) salts such as chromium (III) sulfate, in themselves tanned in a known manner, the pretanned skins ("wet blues") thus obtained and deacidified at a pH of 4 to 7, in particular 4 to 6, and at temperatures of 15 to 50 ° C., in particular 30 to 40 ° C., during a Treated period of 30 to 480 minutes with an aqueous solution of the condensation products.
  • a conventional chromium-containing tannin for example chromium (III) salts such as chromium (III) sulfate
  • the required amount of condensation product based on the shaved weight of the leather, is normally 1 to 30% by weight, in particular 3 to 20% by weight.
  • the liquor length is usually 30 to 200%, based on the fold weight of the leather.
  • the leather After the treatment, the leather is usually fixed at a pH of 3 to 5, for example using an organic acid such as formic acid, and, if desired, dyed and greased.
  • an organic acid such as formic acid
  • the chrome leather retanned according to the invention may additionally have been treated with other tanning agents such as polymer tanning agents or syntans before retanning with the water-soluble condensation products. These condensation products can also be used simultaneously with such additional tanning agents.
  • other tanning agents such as polymer tanning agents or syntans before retanning with the water-soluble condensation products. These condensation products can also be used simultaneously with such additional tanning agents.
  • the leathers produced by the process according to the invention have a high shrinking temperature of over 100 ° C., which is of great importance for the further processing of the leathers.
  • the leathers have good fastness properties such as, above all, high light fastness and have high heat resistance.
  • the leathers produced with the condensation products used according to the invention have a light color, usually ivory to white when used alone. When retanning chrome leather, they significantly lighten the natural color of the chrome leather.
  • a significant advantage of the condensation products used according to the invention is their high level of single-action.
  • Table 2 shows the amounts and the molar ratios of the compounds or solutions used. Table 2 example melamine Glyoxylic acid Caustic soda Glyoxal [G] [mol] [G] [mol] [G] [mol] [G] [mol] 5 126 1 148 1 80 1 145 1 6 126 1 444 3rd 240 3rd 435 3rd 7 126 1 148 1 80 1 435 3rd
  • Table 3 shows the amounts and the molar ratios of the compounds or solutions used. Table 3 example Thiourea Glyoxylic acid Caustic soda Glyoxal water [G] [mol] [G] [mol] [G] [mol] [G] [mol] [G] [mol] [G] [mol] [G] 8th 76 1 148 1 80 1 435 3rd 40 9 76 1 296 2nd 160 2nd 290 2nd 80 10th 76 1 444 3rd 240 3rd 145 1 115
  • Table 7 shows the amounts and the molar ratios of the compounds or solutions used. Table 7 example melamine Glutardialdehyde water [G] [mol] [G] [mol] [G] 37 126 1 1000 5 125 38 126 1 1200 6 125 39 126 1 800 4th 125 40 126 1 600 3rd 125 41 126 1 700 3.5 125 42 126 1 400 2nd 65
  • a mixture of 60 g (1 mol) of urea, 200 g of a 50% strength by weight aqueous glutardialdehyde solution (corresponding to 1 mol of glutardialdehyde) and 60 g of water was heated to 60 ° C. for 1 hour. A water-clear, yellowish solution was obtained.
  • a beetroot blue of the folding thickness 1.8 mm produced in the usual way was rinsed, washed and then deacidified to pH 4.5 with sodium hydrogen carbonate and sodium formate.
  • the leather was then drummed for 60 minutes in a barrel at a liquor length of 100% and a water temperature of 40 ° C. with 8% by weight of the condensation product from Example 6, based on the fold weight of the leather.
  • the leather was then rinsed, dyed with a conventional leather dye, greased with a conventional licker and fixed to a pH of 3.8 with formic acid.
  • the leather produced in this way is suitable, for example, as upper shoe leather.
  • a 1.6 mm thick beef blue made in the usual way was rinsed, washed and then deacidified to a pH of 4.5.
  • the leather was then drummed for 40 minutes in a barrel at a liquor length of 100% and a water temperature of 40 ° C. with 3 wt. -% of the condensation product from Example 12 were added and drummed for a further 60 minutes at the same temperature.
  • the leather was greased with 6% by weight of a conventional synthetic fat liquor, based on the fold weight of the leather, and fixed with formic acid at a pH of 3.8.
  • the leather obtained after the usual completion had a good degree of whiteness in addition to good body and solid grain. It showed very good lightfastness and excellent heat resistance.
  • the leather produced in this way is suitable, for example, as upper shoe leather.
  • Well descaled and pickled bark with a gap thickness of 3 mm was mixed in three portions at a two-hour interval at a liquor length of 50% with 25% by weight of the condensation product from Example 6, based on the gap weight of the pale, and then within 16 Tumbled in the barrel for hours at room temperature and a pH of 3.8. Then a pH of 7 was set with sodium hydrogen carbonate. After a short rinse, the leather was finished as usual.
  • a white leather with a shrinking temperature of 82 ° C. was obtained, which had high light fastness and good heat resistance.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

Solo tanning of pelts and retanning of chrome-tanned leather by using a water-soluble condensation product of A) 1 mol of melamine, dicyandiamide, urea or thiourea or a mixture thereof, B) 0.5 to 12 mol of glyoxylic acid or of an aliphatic dialdehyde having up to 6 carbon atoms or of a mixture thereof, C) 0 to 3 mol of a cocondensable compound having at least one phenolic hydroxyl group or at least one alcoholic hydroxyl group, and D) 0 to 3 mol of a cocondensable compound having an amide or amine group, or the alkali metal or ammonium salts of these condensation products.

Description

Die vorliegende Erfindung betrifft ein verbessertes Verfahren zum Alleingerben von Blößen und zum Nachgerben von Chromleder sowie neue wasserlösliche Kondensationsprodukte und ein Verfahren zu ihrer Herstellung.The present invention relates to an improved process for the sole tanning of pelts and for retanning chrome leather as well as new water-soluble condensation products and a process for their production.

Unter den Gerbeverfahren spielt die Chromgerbung heute immer noch eine dominierende Rolle. Aber mit chromhaltigen Gerbmitteln allein kann man nicht Leder für alle Verwendungszwecke herstellen. Deshalb wird meist eine Kombinationsgerbung durchgeführt, wobei zuerst mit Chromgerbstoffen wie Chrom(III)-Salzen die Hauptgerbung und danach beispielsweise mit vegetabilen oder synthetischen Gerbstoffen eine Nachgerbung erfolgt. Auch werden vegetabile und synthetische Gerbstoffe zur Alleingerbung ohne chromhaltige Gerbmittel eingesetzt.Chrome tanning still plays a dominant role in the tanning process. But tanning agents containing chrome alone cannot make leather for all purposes. For this reason, combination tanning is usually carried out, the main tanning being carried out first with chrome tanning agents such as chromium (III) salts and then retanning with, for example, vegetable or synthetic tanning agents. Vegetable and synthetic tanning agents are also used for single tanning without chrome-containing tanning agents.

Die Verwendung solcher vegetabiler und synthetischer Gerbstoffe führt jedoch in der Regel zu einer Reihe von Nachteilen, beispielsweise zu geringer Lichtechtheit und zu geringer Wärmeresistenz des Leders, Anfärben des Leders durch die Eigenfarbe des Gerbstoffs oder keiner ausreichenden Alleingerbwirkung dieser Mittel.However, the use of such vegetable and synthetic tanning agents generally leads to a number of disadvantages, for example insufficient lightfastness and low heat resistance of the leather, dyeing of the leather due to the inherent color of the tanning agent or insufficient self-acting effect of these agents.

Aufgabe der vorliegenden Erfindung war es daher, Gerbmittel mit verbesserter Alleingerbwirkung bereitzustellen, so daß auf die Mitverwendung von chromhaltigen Gerbemitteln verzichtet werden kann, oder zumindest mit diesen Mitteln zu bewirken, daß in Kombination mit Chromgerbstoffen die Aufhebung der oben beschriebenen Mängel des Standes der Technik erreicht wird.The object of the present invention was therefore to provide tanning agents with an improved single-tanning effect, so that the use of tanning agents containing chromium can be dispensed with, or at least to use these agents to bring about the fact that, in combination with chrome tanning agents, the above-described deficiencies in the prior art are eliminated becomes.

Aus der EP-A 301 406 sind Kondensationsprodukte von Melamin mit Glyoxal und/oder Glyoxylsäure bekannt, die Verbindungen mit einer phenolischen Hydroxylgruppe oder Stickstoffverbindungen miteinkondensiert enthalten können. Diese Kondensationsprodukte werden als Gerbereihilfsmittel für ein chromfreies Gerbeverfahren aber immer in Verbindung mit Aluminium-, Titan- oder Zirkon-haltigen Gerbstoffen empfohlen.From EP-A 301 406 condensation products of melamine with glyoxal and / or glyoxylic acid are known, which may contain compounds with a phenolic hydroxyl group or nitrogen compounds. These condensation products are recommended as tanning aids for a chrome-free tanning process, but always in conjunction with tannins containing aluminum, titanium or zircon.

Aus der FR-A 2 262 056 sind Kondensationsprodukte aus 0,25 bis 0,9 mol Harnstoff und 1 mol Glyoxal bekannt. Sie werden als Hilfsmittel für die Beschichtung von Papier empfohlen.FR-A 2 262 056 discloses condensation products made from 0.25 to 0.9 mol of urea and 1 mol of glyoxal. They are recommended as tools for coating paper.

Demgemäß wurde ein Verfahren zum Alleingerben von Leder und zum Nachgerben von Chromleder gefunden, welches dadurch gekennzeichnet ist, daß man hierzu ein wasserlösliches Kondensationsprodukt aus

  • A) 1 mol Melamin, Dicyandiamid, Harnstoff oder Thioharnstoff oder eines Gemisches dieser Verbindungen,
  • B) 0,5 bis 12 mol Glyoxylsäure oder eines aliphatischen Dialdehyds mit bis zu 6 C-Atomen oder eines Gemisches dieser Verbindungen,
  • C) 0 bis 3 mol einer einkondensierbaren Verbindung mit mindestens einer phenolischen Hydroxylgruppe oder mindestens einer alkoholischen Hydroxylgruppe und
  • D) 0 bis 3 mol einer einkondensierbaren Verbindung mit einer Amid- oder Amin-Gruppierung
oder die Alkalimetall- oder Ammoniumsalze dieser Kondensationsprodukte verwendet.Accordingly, a method for tanning leather alone and for retanning chrome leather has been found, which is characterized in that a water-soluble condensation product is used for this purpose
  • A) 1 mol of melamine, dicyandiamide, urea or thiourea or a mixture of these compounds,
  • B) 0.5 to 12 mol of glyoxylic acid or an aliphatic dialdehyde with up to 6 C atoms or a mixture of these compounds,
  • C) 0 to 3 mol of a condensable compound having at least one phenolic hydroxyl group or at least one alcoholic hydroxyl group and
  • D) 0 to 3 mol of a condensable compound with an amide or amine group
or the alkali metal or ammonium salts of these condensation products are used.

Als Komponente A setzt man bevorzugt Melamin, Dicyandiamid, Harnstoff oder Thioharnstoff allein oder eine Mischung aus 50 bis 95 mol-% Melamin und 5 bis 50 mol-% Dicyandiamid ein. Man kann aber auch Mischungen aus Melamin und Harnstoff, Melamin und Thioharnstoff, Dicyandiamid und Harnstoff, Dicyandiamid und Thioharnstoff und Harnstoff und Thioharnstoff sowie eine Mischung aus drei oder vier der genannten Verbindungen verwenden.Component A is preferably melamine, dicyandiamide, urea or thiourea alone or a mixture of 50 to 95 mol% melamine and 5 to 50 mol% dicyandiamide. However, mixtures of melamine and urea, melamine and thiourea, dicyandiamide and urea, dicyandiamide and thiourea and urea and thiourea and a mixture of three or four of the compounds mentioned can also be used.

Als Komponente B dienen Glyoxalsäure oder ein aliphatischer Dialdehyd mit bis zu 6 C-Atomen wie beispielsweise Glyoxal, Malondialdehyd, Succindialdehyd, Glutardialdehyd oder Adipindialdehyd. Besonders bevorzugt werden Glyoxylsäure, Glyoxal und Glutardialdehyd allein und Mischungen aus Glyoxylsäure und Glyoxal sowie aus Glyoxylsäure und Glutardialdehyd, wobei die beiden Bestandteile in diesen Mischungen mit einem Anteil von jeweils 1 bis 99 mol-%, vorzugsweise 20 bis 80 mol-%, enthalten sind.Glyoxalic acid or an aliphatic dialdehyde with up to 6 carbon atoms, such as, for example, glyoxal, malondialdehyde, succindialdehyde, glutardialdehyde or adipindialdehyde, are used as component B. Glyoxylic acid, glyoxal and glutardialdehyde alone and mixtures of glyoxylic acid and glyoxal and of glyoxylic acid and glutardialdehyde are particularly preferred, the two constituents being present in each of these mixtures in a proportion of 1 to 99 mol%, preferably 20 to 80 mol% .

Die Summe aller Komponenten B liegt zwischen 0,5 und 12 mol, vorzugsweise 2 und 7 mol pro Mol A. Die Glyoxylsäure kann als freie Säure oder in Form ihrer Alkalimetallsalze oder ihres Ammoniumsalzes eingesetzt werden.The sum of all components B is between 0.5 and 12 mol, preferably 2 and 7 mol, per mol of A. The glyoxylic acid can be used as the free acid or in the form of its alkali metal salts or its ammonium salt.

Als einkondensierbare Verbindung C kommen Phenole wie Phenolsulfonsäuren, Sulfosalicylsäuren, Salicylsäure, Resorcin, Brenzkatechin, Hydrochinon, Hydroxychinoline oder Bis(hydroxyphenyl)sulfone sowie Alkohole, insbesondere Kohlenhydrate wie Glucose oder Stärke, in Betracht. Saure Verbindungen können dabei in Form ihre Alkalimetallsalze einkondensiert werden.As the condensable compound C, phenols such as phenolsulfonic acids, sulfosalicylic acids, salicylic acid, resorcinol, pyrocatechol, hydroquinone, hydroxyquinolines or bis (hydroxyphenyl) sulfones and alcohols, in particular carbohydrates such as glucose or starch, are suitable. Acidic compounds can be condensed in the form of their alkali metal salts.

Als einkondensierbare Verbindung D können Carbonsäureamide, Sulfonsäureamide, Carbonsäureimide, substituierte Harnstoffe, Aminosäuren, Iminosäuren sowie Dialkylamine und Dialkanolamine verwendet werden. Beispiele hierfür sind Acetamid, Formamid, Benzoesäureamid, Amidosulfonsäure, Succinimid, Phenylharnstoff, Glycin, Alanin, Phenylglycin, Iminodiessigsäure, Diethylamin, Dipropylamin, Dibutylamin, Diethanolamin oder Diisopropanolamin. Saure Verbindungen können dabei in Form ihrer Alkalimetallsalze einkondensiert werden.Carboxylic acid amides, sulfonic acid amides, carboximides, substituted ureas, amino acids, imino acids and dialkylamines and dialkanolamines can be used as the condensable compound D. Examples include acetamide, formamide, benzoic acid amide, sulfamic acid, Succinimide, phenylurea, glycine, alanine, phenylglycine, iminodiacetic acid, diethylamine, dipropylamine, dibutylamine, diethanolamine or diisopropanolamine. Acidic compounds can be condensed in the form of their alkali metal salts.

Die Verbindungen C und D werden in einer Menge von 0 bis 3 mol, vorzugsweise 0 bis 0,5 mol pro Mol A, einkondensiert.The compounds C and D are condensed in an amount of 0 to 3 mol, preferably 0 to 0.5 mol, per mol of A.

Besonders bevorzugte Kondensationsprodukte setzen sich wie folgt zusammen:

  • 1 mol Melamin und 5 bis 7 mol einer Mischung aus jeweils 15 bis 85 mol-%, vorzugsweise 30 bis 70 mol-% Glyoxylsäure und Glutardialdehyd
  • 1 mol Melamin oder Thioharnstoff und 2 bis 7 mol einer Mischung aus jeweils 5 bis 95 mol-%, vorzugsweise 25 bis 75 mol-% Glyoxylsäure und Glyoxal
  • 1 mol Harnstoff oder Dicyandiamid und 0,5 bis 7 mol einer Mischung aus jeweils 5 bis 95 mol-%, vorzugsweise 25 bis 75 mol-% Glyoxylsäure und Glyoxal
  • 1 mol einer Mischung aus 50 bis 95 mol-% Melamin und 5 bis 50 mol-% Dicyandiamid und 2 bis 12 mol einer Mischung aus jeweils 10 bis 90 mol-%, vorzugsweise 30 bis 70 mol-% Glyoxylsäure und Glyoxal
  • 1 mol Harnstoff und 2 bis 7 mol Glyoxal
  • 1 mol Melamin oder Harnstoff oder Dicyandiamid und 0,5 bis 7 mol Glutardialdehyd
Die im erfindungsgemäßen Verfahren zur Verwendung kommenden Kondensationsprodukte werden durch Kondensation der Komponenten A bis D in den angegebenen Mengen in der Weise hergestellt, daß man alle benötigten Komponenten auf einmal zusammengibt und zum Endprodukt reagieren läßt oder daß man einen Teil der Komponenten vorlegt, miteinander reagieren läßt, eventuell portionsweise danach die restlichen Komponenten zugibt und, gegebenenfalls stufenweise, zum Endprodukt reagieren läßt.Particularly preferred condensation products are composed as follows:
  • 1 mol of melamine and 5 to 7 mol of a mixture of 15 to 85 mol%, preferably 30 to 70 mol%, of glyoxylic acid and glutardialdehyde
  • 1 mol of melamine or thiourea and 2 to 7 mol of a mixture of 5 to 95 mol%, preferably 25 to 75 mol%, of glyoxylic acid and glyoxal
  • 1 mol of urea or dicyandiamide and 0.5 to 7 mol of a mixture of 5 to 95 mol%, preferably 25 to 75 mol%, of glyoxylic acid and glyoxal
  • 1 mol of a mixture of 50 to 95 mol% of melamine and 5 to 50 mol% of dicyandiamide and 2 to 12 mol of a mixture of 10 to 90 mol%, preferably 30 to 70 mol% of glyoxylic acid and glyoxal
  • 1 mol of urea and 2 to 7 mol of glyoxal
  • 1 mol of melamine or urea or dicyandiamide and 0.5 to 7 mol of glutardialdehyde
The condensation products used in the process according to the invention are prepared by condensing the components A to D in the amounts stated in such a way that all the components required are combined at once and allowed to react to the end product or that some of the components are initially introduced and allowed to react with one another , possibly in portions afterwards adding the remaining components and, if necessary in stages, reacting to give the end product.

Die Kondensation erfolgt in wäßriger Lösung bei Temperaturen von 20 bis 100°C, vorzugsweise 30 bis 90°C, und normalerweise bei einem pH-Wert von 1 bis 8. Die Kondensationsreaktion ist im angegebenen Temperaturbereich meist innerhalb von 10 bis 240 Minuten beendet. Man erhält so in der Regel klare wäßrige Harzlösungen, die mit Wasser verdünnbar sind.The condensation takes place in aqueous solution at temperatures of 20 to 100 ° C, preferably 30 to 90 ° C, and usually at a pH of 1 to 8. The condensation reaction is in the temperature range indicated usually finished within 10 to 240 minutes. This generally gives clear aqueous resin solutions which can be diluted with water.

Die erhaltenen Lösungen werden Zweckmäßigerweise auf einen Feststoffgehalt von 10 bis 80 Gew.-%, insbesondere 20 bis 60 Gew.-%, eingestellt und können direkt zum Gerben der Leder bzw. Blößen eingesetzt werden. Man kann die Kondensationsprodukte aber auch nach üblichen Verfahren wie Abdestillieren des Wassers oder durch Sprühtrocknung in Pulverform erhalten. Die Kondensationsprodukte können, sofern sie saure Gruppen tragen, in ihre Alkalimetall- oder Ammoniumsalze überführt werden.The solutions obtained are expediently adjusted to a solids content of 10 to 80% by weight, in particular 20 to 60% by weight, and can be used directly for tanning the leather or pelts. However, the condensation products can also be obtained in powder form by customary processes, such as distilling off the water or by spray drying. If they carry acidic groups, the condensation products can be converted into their alkali metal or ammonium salts.

Gegenstand der vorliegenden Erfindung sind auch neue wasserlösliche Kondensationsprodukte aus

  • A') 1 mol Dicyandiamin, Harnstoff oder Thioharnstoff oder eines Gemisches dieser Verbindungen untereinander oder mit bis zu einem Anteil von 0,8 mol Melamin,
  • B) 0,5 bis 12 mol, vorzugsweise 2 bis 7 mol der Komponente B,
  • C) 0 bis 3 mol, vorzugsweise 0 bis 0,5 mol der Komponente C und
  • D) 0 bis 3 mol, vorzugsweise 0 bis 0,5 mol der Komponente D
mit Ausnahme von Kondensationsprodukten aus 0,25 bis 0,9 mol Harnstoff und 1 mol Glyoxal,
welche eine Untergruppe der im erfindungsgemäßen Verfahren zur Verwendung kommenden Kondensationsprodukte darstellen.The present invention also relates to new water-soluble condensation products
  • A ') 1 mol of dicyandiamine, urea or thiourea or a mixture of these compounds with one another or with up to a proportion of 0.8 mol of melamine,
  • B) 0.5 to 12 mol, preferably 2 to 7 mol, of component B,
  • C) 0 to 3 mol, preferably 0 to 0.5 mol of component C and
  • D) 0 to 3 mol, preferably 0 to 0.5 mol, of component D.
with the exception of condensation products from 0.25 to 0.9 mol urea and 1 mol glyoxal,
which represent a subset of the condensation products used in the process according to the invention.

Die genannten neuen wasserlöslichen Kondensationsprodukte werden wie oben beschrieben durch Kondensation in wäßriger Lösung bei 20 bis 100°C hergestellt.The new water-soluble condensation products mentioned are prepared as described above by condensation in aqueous solution at 20 to 100 ° C.

Das erfindungsgemäße Gerbeverfahren eignet sich in hervorragender Weise zum Alleingerben von Blößen in wäßriger Flotte. Hierbei geht man zweckmäßigerweise so vor, daß die gepickelten Blößen, beispielsweise Rindsblößen mit einer Spaltstärke von 1,5 bis 4 mm, bei einem pH-Wert von 2 bis 5, insbesondere 2,5 bis 4, und bei einer Temperatur von 15 bis 50°C, insbesondere 20 bis 30°C, während eines Zeitraumes von 5 bis 30 Stunden mit einer wäßrigen Lösung der Kondensationsprodukte behandelt werden. Die Behandlung erfolgt beispielsweise durch Walken in einem Faß. Die benötigte Menge an Kondensationsprodukt beträgt normalerweise, bezogen auf das Blößengewicht, 5 bis 50 Gew.-%, insbesondere 10 bis 30 Gew.-%. Die Flottenlänge, d.h. das prozentuale Gewichtsverhältnis der Behandlungsflotte zur Ware, beträgt üblicherweise 30 bis 200 %, bezogen auf das Blößengewicht.The tanning process according to the invention is outstandingly suitable for tanning pelts alone in an aqueous liquor. Appropriately, the procedure is such that the pickled pelts, for example beef pelts with a gap thickness of 1.5 to 4 mm, at a pH of 2 to 5, in particular 2.5 to 4, and at a temperature of 15 to 50 ° C, in particular 20 to 30 ° C, are treated with an aqueous solution of the condensation products for a period of 5 to 30 hours. The treatment takes place, for example, by drumming in a barrel. The required amount of condensation product is normally 5 to 50% by weight, in particular 10 to 30% by weight, based on the pelt weight. The liquor length, ie the percentage weight ratio of the treatment liquor to the goods, is usually 30 to 200%, based on the weight of the naked body.

Nach erfolgter Behandlung wird das Leder üblicherweise auf einen pH-Wert von 4 bis 8 eingestellt, wozu man beispielsweise Natriumhydrogencarbonat verwendet, und gewünschtenfalls gefärbt und gefettet.After the treatment has taken place, the leather is usually adjusted to a pH of 4 to 8, for which purpose sodium bicarbonate is used, for example, and, if desired, colored and greased.

Das erfindungsgemäße Gerbeverfahren eignet sich ebenfalls in hervorragender Weise zum Nachgerben von Chromleder in wäßriger Flotte. Es wird in der Regel so durchgeführt, daß man die gepickelten Blößen, beispielsweise Rindsblößen mit Spaltstärken von 1,5 bis 4 mm, mit einem üblichen chromhaltigen Gerbstoff, beispielsweise Chrom(III)-Salzen wie Chrom(III)-sulfat, in an sich bekannter Weise gerbt, die so erhaltenen vorgegerbten Häute ("Wetblues") entsäuert und bei einem pH-Wert von 4 bis 7, insbesondere 4 bis 6, und bei Temperaturen von 15 bis 50°C, insbesondere 30 bis 40°C, während eines Zeitraumes von 30 bis 480 Minuten mit einer wäßrigen Lösung der Kondensationsprodukte behandelt. Diese Behandlung erfolgt beispielsweise durch Walken in einem Faß. Die benötigte Menge an Kondensationsprodukt beträgt normalerweise, bezogen auf das Falzgewicht des Leders, 1 bis 30 Gew.-%, insbesondere 3 bis 20 Gew.-%. Die Flottenlänge beträgt üblicherweise 30 bis 200 %, bezogen auf das Falzgewicht des Leders.The tanning process according to the invention is also outstandingly suitable for retanning chrome leather in an aqueous liquor. It is usually carried out in such a way that the pickled pelts, for example beef pelts with a gap thickness of 1.5 to 4 mm, with a conventional chromium-containing tannin, for example chromium (III) salts such as chromium (III) sulfate, in themselves tanned in a known manner, the pretanned skins ("wet blues") thus obtained and deacidified at a pH of 4 to 7, in particular 4 to 6, and at temperatures of 15 to 50 ° C., in particular 30 to 40 ° C., during a Treated period of 30 to 480 minutes with an aqueous solution of the condensation products. This treatment takes place, for example, by drumming in a barrel. The required amount of condensation product, based on the shaved weight of the leather, is normally 1 to 30% by weight, in particular 3 to 20% by weight. The liquor length is usually 30 to 200%, based on the fold weight of the leather.

Nach erfolgter Behandlung wird das Leder üblicherweise bei einem pH-Wert von 3 bis 5 fixiert, wozu man beispielsweise eine organische Säure wie Ameisensäure verwendet, und gewünschtenfalls gefärbt und gefettet.After the treatment, the leather is usually fixed at a pH of 3 to 5, for example using an organic acid such as formic acid, and, if desired, dyed and greased.

Das erfindungsgemäß nachgegerbte Chromleder kann vor der Nachgerbung mit den wasserlöslichen Kondensationsprodukten zusätzlich mit anderen Gerbemitteln wie Polymergerbstoffen oder Syntanen behandelt worden sein. Auch können diese Kondensationsprodukte gleichzeitig mit derartigen zusätzlichen Gerbemitteln eingesetzt werden.The chrome leather retanned according to the invention may additionally have been treated with other tanning agents such as polymer tanning agents or syntans before retanning with the water-soluble condensation products. These condensation products can also be used simultaneously with such additional tanning agents.

Die nach dem erfindungsgemäßen Verfahren hergestellten Leder haben eine hohe Schrumpfungstemperatur von über 100°C, was für die weitere Verarbeitung des Leders von großer Bedeutung ist. Die Leder weisen gute Echtheitseigenschaften wie vor allem hohe Lichtechtheiten auf und haben hohe Wärmeresistenzen. Auch tritt der Nachteil einer gelben bis braunen Eigenfarbe wie beispielsweise bei Verwendung von vegetabilen Nachgerbstoffen nicht mehr auf. Die mit den erfindungsgemäß eingesetzten Kondensationsprodukten hergestellten Leder haben eine helle Farbe, bei Alleingerbung meist elfenbeinfarbig bis weiß. Bei Nachgerbung von Chromleder hellen sie die Eigenfarbe des Chromleders deutlich auf. Ein wesentlicher Vorteil der erfindungsgemäß eingesetzen Kondensationsprodukte ist ihre hohe Alleingerbwirkung.The leathers produced by the process according to the invention have a high shrinking temperature of over 100 ° C., which is of great importance for the further processing of the leathers. The leathers have good fastness properties such as, above all, high light fastness and have high heat resistance. The disadvantage of a yellow to brown intrinsic color, such as when using vegetable retanning agents, no longer occurs. The leathers produced with the condensation products used according to the invention have a light color, usually ivory to white when used alone. When retanning chrome leather, they significantly lighten the natural color of the chrome leather. A significant advantage of the condensation products used according to the invention is their high level of single-action.

HerstellungsbeispielManufacturing example Beispiele 1 bis 4Examples 1 to 4 Kondensationsprodukte aus Melamin, Glyoxylsäure und GlutardialdehydCondensation products from melamine, glyoxylic acid and glutardialdehyde

Mischungen aus Melamin, 50 gew.-%iger Glyoxylsäurelösung und 50 gew.-%iger Natronlauge wurden 1 Stunde auf 60°C erwärmt. Nach Abkühlung der klaren Lösung auf 40°C wurde anschließend 50 gew.-%ige wäßrige Glutardialdehydlösung zugegeben und 1 Stunde bei 40°C gehalten. Man erhielt klare, wasserverdünnbare Harzlösungen. Tabelle 1 zeigt die Mengen und die Molverhältnisse der eingesetzten Verbindungen bzw. Lösungen. Tabelle 1 Beispiel Melamin Glyoxylsäure Natronlauge Glutardialaldehyd [g] [mol] [g] [mol] [g] [mol] [g] [mol] 1 126 1 444 3 240 3 600 3 2 126 1 296 2 160 2 800 4 3 126 1 592 4 320 4 400 2 4 126 1 740 5 400 5 200 1 Mixtures of melamine, 50% by weight glyoxylic acid solution and 50% by weight sodium hydroxide solution were heated to 60 ° C. for 1 hour. After the clear solution had cooled to 40 ° C., 50% strength by weight aqueous glutardialdehyde solution was then added and the mixture was kept at 40 ° C. for 1 hour. Clear, water-dilutable resin solutions were obtained. Table 1 shows the amounts and the molar ratios of the compounds or solutions used. Table 1 example melamine Glyoxylic acid Caustic soda Glutardialaldehyde [G] [mol] [G] [mol] [G] [mol] [G] [mol] 1 126 1 444 3rd 240 3rd 600 3rd 2nd 126 1 296 2nd 160 2nd 800 4th 3rd 126 1 592 4th 320 4th 400 2nd 4th 126 1 740 5 400 5 200 1

Beispiele 5 bis 7Examples 5 to 7 Kondensationsprodukte aus Melamin, Glyoxylsäure und GlyoxalCondensation products from melamine, glyoxylic acid and glyoxal

Mischungen aus Melamin, 50 gew.-%iger Glyoxylsäurelösung, 50 gew.-%iger Natronlauge und 40 gew.-%iger wäßriger Glyoxallösung wurden 1 Stunde auf 60°C erwärmt. Man erhielt klare, wasserverdünnbare Harzlösungen. Tabelle 2 zeigt die Mengen und die Molverhältnisse der eingesetzten Verbindungen bzw. Lösungen. Tabelle 2 Beispiel Melamin Glyoxylsäure Natronlauge Glyoxal [g] [mol] [g] [mol] [g] [mol] [g] [mol] 5 126 1 148 1 80 1 145 1 6 126 1 444 3 240 3 435 3 7 126 1 148 1 80 1 435 3 Mixtures of melamine, 50% by weight glyoxylic acid solution, 50% by weight sodium hydroxide solution and 40% by weight aqueous glyoxal solution were heated to 60 ° C. for 1 hour. Clear, water-dilutable resin solutions were obtained. Table 2 shows the amounts and the molar ratios of the compounds or solutions used. Table 2 example melamine Glyoxylic acid Caustic soda Glyoxal [G] [mol] [G] [mol] [G] [mol] [G] [mol] 5 126 1 148 1 80 1 145 1 6 126 1 444 3rd 240 3rd 435 3rd 7 126 1 148 1 80 1 435 3rd

Beispiele 8 bis 10Examples 8-10 Kondensationsprodukte aus Thioharnstoff, Glyoxylsäure und GlyoxalCondensation products from thiourea, glyoxylic acid and glyoxal

Mischungen aus Thioharnstoff, 50 gew.-%iger Glyoxylsäurelösung, 50 gew.-%iger Natronlauge, 40 gew.-%iger wäßriger Glyoxallösung und Wasser wurden 1 Stunde auf 65°C erwärmt. Man erhielt klare, wasserverdünnbare Harzlösungen. Tabelle 3 zeigt die Mengen und die Molverhältnisse der eingesetzten Verbindungen bzw. Lösungen. Tabelle 3 Beispiel Thioharnstoff Glyoxylsäure Natronlauge Glyoxal Wasser [g] [mol] [g] [mol] [g] [mol] [g] [mol] [g] 8 76 1 148 1 80 1 435 3 40 9 76 1 296 2 160 2 290 2 80 10 76 1 444 3 240 3 145 1 115 Mixtures of thiourea, 50% by weight glyoxylic acid solution, 50% by weight sodium hydroxide solution, 40% by weight aqueous glyoxal solution and water were heated to 65 ° C. for 1 hour. Clear, water-dilutable resin solutions were obtained. Table 3 shows the amounts and the molar ratios of the compounds or solutions used. Table 3 example Thiourea Glyoxylic acid Caustic soda Glyoxal water [G] [mol] [G] [mol] [G] [mol] [G] [mol] [G] 8th 76 1 148 1 80 1 435 3rd 40 9 76 1 296 2nd 160 2nd 290 2nd 80 10th 76 1 444 3rd 240 3rd 145 1 115

Beispiele 11 bis 16Examples 11 to 16 Kondensationsprodukte aus Harnstoff, Glyoxylsäure und GlyoxalCondensation products from urea, glyoxylic acid and glyoxal

Mischungen aus Harnstoff, 50 gew.-%iger Glyoxylsäurelösung, 50 gew.-%iger Natronlauge und 40 gew.-%iger wäßriger Glyoxallösung wurden 1 Stunde auf 60°C erwärmt. Man erhielt klare, wasserverdünnbare Harzlösungen. Tabelle 4 zeigt die Mengen und die Molverhältnisse der eingesetzten Verbindungen bzw. Lösungen. Tabelle 4 Beispiel Harnstoff Glyoxylsäure Natronlauge Glyoxal [g] [mol] [g] [mol] [g] [mol] [g] [mol] 11 60 1 148 1 80 1 435 3 12 60 1 296 2 160 2 290 2 13 60 1 444 3 240 3 145 1 14 60 1 148 1 80 1 290 2 15 60 1 74 0,5 40 0,5 145 1 16 60 1 74 0,5 40 0,5 73 0,5 Mixtures of urea, 50% by weight glyoxylic acid solution, 50% by weight sodium hydroxide solution and 40% by weight aqueous glyoxal solution were heated to 60 ° C. for 1 hour. Clear, water-dilutable resin solutions were obtained. Table 4 shows the amounts and the molar ratios of the compounds or solutions used. Table 4 example urea Glyoxylic acid Caustic soda Glyoxal [G] [mol] [G] [mol] [G] [mol] [G] [mol] 11 60 1 148 1 80 1 435 3rd 12th 60 1 296 2nd 160 2nd 290 2nd 13 60 1 444 3rd 240 3rd 145 1 14 60 1 148 1 80 1 290 2nd 15 60 1 74 0.5 40 0.5 145 1 16 60 1 74 0.5 40 0.5 73 0.5

Beispiele 17 bis 27Examples 17 to 27 Kondensationsprodukte aus Dicyandiamid, Glyoxylsäure und GlyoxalCondensation products from dicyandiamide, glyoxylic acid and glyoxal

Mischungen aus Dicyandiamid, 50 gew.-%iger Glyoxylsäurelösung, 50 gew.-%iger Natronlauge und Wasser wurden 4 Stunden auf 60°C erwärmt. Anschließend wurde auf 40°C abgekühlt, mit 40 gew.-%iger wäßriger Glyoxallösung versetzt und 1 Stunde bei 40°C gehalten. Man erhielt klare, wasserverdünnbare Harzlösungen. Tabelle 5 zeigt die Mengen und die Molverhältnisse der eingesetzten Verbindungen bzw. Lösungen. Tabelle 5 Beispiel Dicyandiamid Glyoxylsäure Natronlauge Glyoxal Wasser [g] [mol] [g] [mol] [g] [mol] [g] [mol] [g] 17 84 1 296 2 160 2 290 2 150 18 84 1 148 1 80 1 290 2 140 19 84 1 444 3 240 3 435 3 170 20 84 1 444 3 240 3 290 2 170 21 84 1 444 3 240 3 145 1 170 22 84 1 592 4 320 4 290 2 175 23 84 1 592 4 320 4 145 1 175 24 84 1 296 2 160 2 580 4 145 25 84 1 296 2 160 2 435 3 155 26 84 1 74 0,5 40 0,5 145 1 135 27 84 1 74 0,5 40 0,5 73 0,5 135 Mixtures of dicyandiamide, 50% by weight glyoxylic acid solution, 50% by weight sodium hydroxide solution and water were heated to 60 ° C. for 4 hours. The mixture was then cooled to 40 ° C., 40% by weight aqueous glyoxal solution was added and the mixture was kept at 40 ° C. for 1 hour. Clear, water-dilutable resin solutions were obtained. Table 5 shows the amounts and the molar ratios of the compounds or solutions used. Table 5 example Dicyandiamide Glyoxylic acid Caustic soda Glyoxal water [G] [mol] [G] [mol] [G] [mol] [G] [mol] [G] 17th 84 1 296 2nd 160 2nd 290 2nd 150 18th 84 1 148 1 80 1 290 2nd 140 19th 84 1 444 3rd 240 3rd 435 3rd 170 20th 84 1 444 3rd 240 3rd 290 2nd 170 21 84 1 444 3rd 240 3rd 145 1 170 22 84 1 592 4th 320 4th 290 2nd 175 23 84 1 592 4th 320 4th 145 1 175 24th 84 1 296 2nd 160 2nd 580 4th 145 25th 84 1 296 2nd 160 2nd 435 3rd 155 26 84 1 74 0.5 40 0.5 145 1 135 27 84 1 74 0.5 40 0.5 73 0.5 135

Beispiele 28 bis 35Examples 28-35 Kondensationsprodukte aus Melamin, Dicyandiamid, Glyoxylsäure und GlyoxalCondensation products from melamine, dicyandiamide, glyoxylic acid and glyoxal

Mischungen aus Melamin, Dicyandiamid, 50 gew.-%iger wäßriger Glyoxylsäurelösung, 40 gew.-%iger wäßriger Glyoxallösung und Wasser wurden 1 Stunde auf 65°C erwärmt. Man erhielt klare, wasserverdünnbare Harzlösungen. Tabelle 6 zeigt die Mengen und die Molverhältnisse der eingesetzten Verbindungen bzw. Lösungen. Tabelle 6 Beispiel Melamin Dicyandiamid Glyoxylsäure Glyoxal Wasser [g] [mol] [g] [mol] [g] [mol] [g] [mol] [g] 28 115 0,91 7,6 0,09 444 3 435 3 295 29 103 0,82 15,1 0,18 444 3 435 3 290 30 92 0,73 22,7 0,27 444 3 435 3 295 31 81 0,64 30,3 0,36 444 3 435 3 275 32 63 0,5 42 0,5 444 3 435 3 270 33 63 0,5 42 0,5 888 6 870 6 395 34 63 0,5 42 0,5 370 2,5 363 2,5 250 35 95 0,75 21 0,25 407 2,75 399 2,75 190 Mixtures of melamine, dicyandiamide, 50% by weight aqueous glyoxylic acid solution, 40% by weight aqueous glyoxal solution and water were heated to 65 ° C. for 1 hour. Clear, water-dilutable resin solutions were obtained. Table 6 shows the amounts and the molar ratios of the compounds or solutions used. Table 6 example melamine Dicyandiamide Glyoxylic acid Glyoxal water [G] [mol] [G] [mol] [G] [mol] [G] [mol] [G] 28 115 0.91 7.6 0.09 444 3rd 435 3rd 295 29 103 0.82 15.1 0.18 444 3rd 435 3rd 290 30th 92 0.73 22.7 0.27 444 3rd 435 3rd 295 31 81 0.64 30.3 0.36 444 3rd 435 3rd 275 32 63 0.5 42 0.5 444 3rd 435 3rd 270 33 63 0.5 42 0.5 888 6 870 6 395 34 63 0.5 42 0.5 370 2.5 363 2.5 250 35 95 0.75 21 0.25 407 2.75 399 2.75 190

Beispiele 36Examples 36 Kondensationsprodukt aus Harnstoff und GlyoxalCondensation product from urea and glyoxal

Eine Mischung aus 60 g (1 mol) Harnstoff und 580 g einer 40 gew.-%igen Glyoxallösung (entsprechend 4 mol Glyoxal) wurde 2 Stunden auf 45°C erwärmt. Man erhielt eine klare Harzlösung.A mixture of 60 g (1 mol) of urea and 580 g of a 40% by weight glyoxal solution (corresponding to 4 mol of glyoxal) was heated to 45 ° C. for 2 hours. A clear resin solution was obtained.

Beispiele 37 bis 42Examples 37 to 42 Kondensationsprodukte aus Melamin und GlutardialdehydCondensation products from melamine and glutardialdehyde

Mischungen aus Melamin, 50 gew.-%iger Glutardialdehydlösung und Wasser wurden 1,5 Stunden auf 60°C erwärmt. Nach Abfiltrieren einer geringen Menge eines farblosen Niederschlags erhielt man klare Harzlösungen. Tabelle 7 zeigt die Mengen und die Molverhältnisse der eingesetzten Verbindungen bzw. Lösungen. Tabelle 7 Beispiel Melamin Glutardialdehyd Wasser [g] [mol] [g] [mol] [g] 37 126 1 1000 5 125 38 126 1 1200 6 125 39 126 1 800 4 125 40 126 1 600 3 125 41 126 1 700 3,5 125 42 126 1 400 2 65 Mixtures of melamine, 50 wt .-% glutardialdehyde solution and water were heated to 60 ° C for 1.5 hours. After filtering off a small amount of a colorless precipitate, clear resin solutions were obtained. Table 7 shows the amounts and the molar ratios of the compounds or solutions used. Table 7 example melamine Glutardialdehyde water [G] [mol] [G] [mol] [G] 37 126 1 1000 5 125 38 126 1 1200 6 125 39 126 1 800 4th 125 40 126 1 600 3rd 125 41 126 1 700 3.5 125 42 126 1 400 2nd 65

Beispiele 43Examples 43 Kondensationsprodukt aus Harnstoff und GlutardialdehydCondensation product from urea and glutardialdehyde

Eine Mischung aus 60 g (1 mol) Harnstoff, 200 g einer 50 gew.-%igen wäßrigen Glutardialdehydlösung (entsprechend 1 mol Glutardialdehyd) und 60 g Wasser wurde 1 Stunde auf 60°C erwärmt. Man erhielt eine wasserklare, gelbliche Lösung.A mixture of 60 g (1 mol) of urea, 200 g of a 50% strength by weight aqueous glutardialdehyde solution (corresponding to 1 mol of glutardialdehyde) and 60 g of water was heated to 60 ° C. for 1 hour. A water-clear, yellowish solution was obtained.

Beispiele 44Examples 44 Kondensationsprodukt aus Dicyandiamid und GlutardialdehydCondensation product of dicyandiamide and glutardialdehyde

Eine Mischung aus 84 g (1 mol) Dicyandiamid, 200 g einer 50 gew.-%igen wäßrigen Glutardialdehydlösung (entsprechend 1 mol Glutardialdehyd) und 84 g Wasser wurde 1 Stunde auf 60°C erwärmt. Man erhielt eine wasserklare, gelbliche Lösung.A mixture of 84 g (1 mol) of dicyandiamide, 200 g of a 50% by weight aqueous glutardialdehyde solution (corresponding to 1 mol of glutardialdehyde) and 84 g of water was heated to 60 ° C. for 1 hour. A water-clear, yellowish solution was obtained.

AnwendungsbeispieleExamples of use Beispiel 45Example 45 Nachgerbung von ChromlederRetanning chrome leather

Ein in üblicher Weise hergestelltes Rindwetblue der Falzstärke 1,8 mm wurde gespült, gewaschen und anschließend mit Natriumhydrogencarbonat und Natriumformiat auf einen pH-Wert von 4,5 entsäuert. Danach wurde das Leder bei einer Flottenlänge von 100 % und einer Wassertemperatur von 40°C mit 8 Gew.-% des Kondensationsproduktes aus Beispiel 6, bezogen auf das Falzgewicht des Leders, 60 Minuten im Faß gewalkt. Anschließend wurde das Leder gespült, mit einem üblichen Lederfarbstoff gefärbt, mit einem üblichen Licker gefettet und mit Ameisensäure auf einem pH-Wert von 3,8 fixiert.A beetroot blue of the folding thickness 1.8 mm produced in the usual way was rinsed, washed and then deacidified to pH 4.5 with sodium hydrogen carbonate and sodium formate. The leather was then drummed for 60 minutes in a barrel at a liquor length of 100% and a water temperature of 40 ° C. with 8% by weight of the condensation product from Example 6, based on the fold weight of the leather. The leather was then rinsed, dyed with a conventional leather dye, greased with a conventional licker and fixed to a pH of 3.8 with formic acid.

Nach üblicher Fertigstellung erhielt man ein gut gefülltes, weiches Leder mit enganliegenden, glatten Narben und wenig aufgehellter Färbung.After the usual completion, a well-filled, soft leather with close-fitting, smooth scars and a little lightened color was obtained.

Das so hergestellte Leder eignet sich beispielsweise als Schuhoberleder.The leather produced in this way is suitable, for example, as upper shoe leather.

Beispiel 46Example 46 Nachgerbung von mit Polymergerbstoffen behandeltem ChromlederRetanning chrome leather treated with polymer tanning agents

Ein in üblicher Weise hergestelltes Rindwetblue der Falzstärke 1,6 mm wurde gespült, gewaschen und anschließend auf einen pH-Wert von 4,5 entsäuert. Danach wurde das Leder bei einer Flottenlänge von 100 % und einer Wassertemperatur von 40°C mit 3 Gew.-% eines üblichen Polymergerbstoffes auf Acrylsäurebasis, bezogen auf das Falzgewicht des Leders, 40 Minuten im Faß gewalkt, anschließend in gleicher Flotte mit 6 Gew.-% des Kondensationsproduktes aus Beispiel 12 versetzt und weitere 60 Minuten bei der gleichen Temperatur gewalkt. Nach kurzem Spülen wurde das Leder mit 6 Gew.-% eines üblichen synthetischen Fettlickers, bezogen auf das Falzgewicht des Leders, gefettet und mit Ameisensäure bei einem PH-Wert von 3,8 fixiert.A 1.6 mm thick beef blue made in the usual way was rinsed, washed and then deacidified to a pH of 4.5. The leather was then drummed for 40 minutes in a barrel at a liquor length of 100% and a water temperature of 40 ° C. with 3 wt. -% of the condensation product from Example 12 were added and drummed for a further 60 minutes at the same temperature. After a brief rinse, the leather was greased with 6% by weight of a conventional synthetic fat liquor, based on the fold weight of the leather, and fixed with formic acid at a pH of 3.8.

Das nach üblicher Fertigstellung erhaltene Leder wies neben guter Fülle und Festnarbigkeit einen hohen Weißgrad auf. Es zeigte eine sehr gute Lichtechtheit und hervorragende Wärmeresistenz.The leather obtained after the usual completion had a good degree of whiteness in addition to good body and solid grain. It showed very good lightfastness and excellent heat resistance.

Das so hergestellte Leder eignet sich beispielsweise als Schuhoberleder.The leather produced in this way is suitable, for example, as upper shoe leather.

Beispiel 47Example 47 Alleingerbung von RindsblößenSolitary barking

Gut entkälkte und gepickelte Rindsblöße mit einer Spaltstärke von 3 mm wurde bei einer Flottenlänge von 50 % mit 25 Gew.-% des Kondensationsprodukte aus Beispiel 6, bezogen auf das Spaltgewicht der Blöße, in drei Portionen in jeweils zweistündigem Abstand versetzt und anschließend innerhalb von 16 Stunden bei Raumtemperatur und einem pH-Wert von 3,8 im Faß gewalkt. Danach wurde mit Natriumhydrogencarbonat ein pH-Wert von 7 eingestellt. Nach kurzem Spülen wurde das Leder wie üblich fertiggestellt.Well descaled and pickled bark with a gap thickness of 3 mm was mixed in three portions at a two-hour interval at a liquor length of 50% with 25% by weight of the condensation product from Example 6, based on the gap weight of the pale, and then within 16 Tumbled in the barrel for hours at room temperature and a pH of 3.8. Then a pH of 7 was set with sodium hydrogen carbonate. After a short rinse, the leather was finished as usual.

Man erhielt ein weißes Leder mit einer Schrumpfungstemperatur von 82°C, das eine hohe Lichtechtheit und eine gute Wärmeresistenz aufwies.A white leather with a shrinking temperature of 82 ° C. was obtained, which had high light fastness and good heat resistance.

Claims (4)

  1. A process for self-tanning pelts and for retanning chrome leather, wherein a water-soluble condensate of
    A) 1 mol of melamine, dicyandiamide, urea or thiourea or of a mixture of these compounds,
    B) from 0.5 to 12 mol of glyoxylic acid or of an aliphatic dialdehyde of up to 6 carbon atoms or of a mixture of these compounds,
    C) from 0 to 3 mol of a compound which can be subjected to a condensation reaction and has at least one phenolic hydroxyl group or at least one alcoholic hydroxyl group and
    D) from 0 to 3 mol of a compound which can be subjected to a condensation reaction and has an amido or amino group,
    or an alkali metal salt or ammonium salt of this condensate, is used for this purpose.
  2. A process for self-tanning pelts and for retanning chrome leather as claimed in claim 1, wherein a water-soluble condensate which is composed of glyoxylic acid, glyoxal or glutardialdehyde or of a mixture of glyoxylic acid and glyoxal or of glyoxylic acid and glutardialdehyde as component B is used for this purpose.
  3. A process for the preparation of a water-soluble condensate, with the exception of condensates of from 0.25 to 0.9 mol of urea and 1 mol of glyoxal, as claimed in claim 1 or 2, wherein
    A') 1 mol of dicyandiamide, urea or thiourea or of a mixture of these compounds with one another or with up to 0.8 mol of melamine is condensed with
    B) from 0.5 to 12 mol of component B,
    C) from 0 to 3 mol of component C and
    D) from 0 to 3 mol of component D
    at from 20 to 100°C in aqueous solution.
EP90119881A 1989-10-27 1990-10-17 Method of tanning hides and retanning chrome-tanned leather Expired - Lifetime EP0429830B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3935879 1989-10-27
DE3935879A DE3935879A1 (en) 1989-10-27 1989-10-27 METHOD FOR GIVING ONLY BLOSSOMS AND GIVING BACK CHROME LEATHER

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EP0429830A2 EP0429830A2 (en) 1991-06-05
EP0429830A3 EP0429830A3 (en) 1992-07-08
EP0429830B1 true EP0429830B1 (en) 1995-03-15

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EP90119881A Expired - Lifetime EP0429830B1 (en) 1989-10-27 1990-10-17 Method of tanning hides and retanning chrome-tanned leather

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EP (1) EP0429830B1 (en)
AT (1) ATE119945T1 (en)
DE (2) DE3935879A1 (en)
ES (1) ES2068965T3 (en)

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DE4108139A1 (en) * 1991-03-13 1992-09-17 Boehme Chem Fab Kg Leather or fur tanning - using condensate of melamine, para-formaldehyde, poly:hydric alcohol and di- or tri-alkanolamine
DE4131202A1 (en) * 1991-09-19 1993-03-25 Bayer Ag METHOD FOR PRODUCING CHROME LEATHER
AT397958B (en) * 1992-05-08 1994-08-25 Chemie Linz Gmbh USE OF CONDENSATION PRODUCTS MELAMINE AND GLYOXYLIC ACID AS ADDITIVES FOR HYDRAULIC BINDERS AND BUILDING MATERIAL
DE4217181A1 (en) * 1992-05-23 1993-11-25 Chemie Linz Deutschland Melamine glyoxylic acid or salt condensate use in hydraulic binder - to increase flow, retard setting and opt. increase strength of set prod.
DE19627531B4 (en) * 1996-07-09 2006-11-02 Construction Research & Technology Gmbh Water-soluble formaldehyde-free polycondensation products based on amino-s-triazines
DE10322107B4 (en) * 2003-03-26 2005-09-08 Ami-Agrolinz Melamine International Gmbh Aminotriazine condensation product, use of an aminotriazine condensation product and process for the preparation of the aminotriazine condensation product
US7034086B2 (en) 2003-03-31 2006-04-25 Cytec Technology Corp. Melamine and guanamine-based crosslinking composition
US7381347B2 (en) 2003-03-31 2008-06-03 Cytec Technology Corp. Crosslinking composition
US7169881B2 (en) 2004-10-29 2007-01-30 Clariant (France) Aminoplast resin compositions
DE102006029408A1 (en) * 2006-06-23 2007-12-27 Lanxess Deutschland Gmbh Condensation products containing sulfonic or carboxylic acid groups and based on di-aldehyde and amino compounds, e.g. glutaraldehyde and melamine and-or urea, used for tanning leather and furs
DE102013014641B4 (en) 2013-09-04 2018-07-12 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Wood product or natural fiber composite product and use of a formaldehyde-free aminoplast resin for their preparation
WO2015086034A1 (en) * 2013-12-12 2015-06-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Wood product or natural fiber composite material product and use of a formaldehyde-free amino- and amide resin based on glyoxylic acid esters for the production thereof

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US3917659A (en) * 1974-07-27 1975-11-04 Union Carbide Corp Solid glyoxal-urea products
DE3724868A1 (en) * 1987-07-28 1989-02-09 Basf Ag TANNING AIDS, THE USE THEREOF AND METHOD FOR TANNING LEATHER

Also Published As

Publication number Publication date
EP0429830A3 (en) 1992-07-08
ES2068965T3 (en) 1995-05-01
DE3935879A1 (en) 1991-05-02
DE59008711D1 (en) 1995-04-20
ATE119945T1 (en) 1995-04-15
EP0429830A2 (en) 1991-06-05

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